Stabilized infrared absorbing dispersions

ABSTRACT

A dispersion, a resin containing the dispersion and polymer film formed from the resin are disclosed. The dispersion includes an infrared light absorbing pigment including organo-metallic particles being less than 1.5 micrometer or less than one micrometer in size. The dispersion also includes a dispersant including phosphorus and a polyol.

BACKGROUND

Multilayer optical film can include oriented layers that can besemi-crystalline and the birefringence of these layers provides largeincreases in the optical power over isotropic polymeric multilayers.Heating these multilayer optical films can at least partially melt theoriented material in order to reduce or remove the birefringence of theoriented optical layers, resulting in a reduction in the optical powerof their reflection bands. In one useful case, the multilayer opticalfilms include an infrared light absorbing dye or pigment. Thesemultilayer optical films can thus absorb radiant energy, e.g. of aninfrared light laser, selectively melting the oriented material in theoptical packet containing the absorber, and reducing the reflectivity ofthat optical packet. Images can be constructed by selective exposure ofthe infrared light to the multilayer optical films. In this manner,controlled spatial patterning of the reflectivity across the multilayeroptical film can be accomplished.

Simple addition of the un-dispersed infrared light absorber in powderform to the film resin can lead to process disruptions and reduced filmquality. For example, large particles can cause flow defects thatmanifest as streaks, mottling, parabolically shaped flow lines or othermarks, disrupting the uniformity, appearance and/or the performance ofthe cast and also drawn film. The variability of infrared light absorberwithin the film leads to uncertainty in the radiation exposureconditions needed for selective melting and imaging of the multilayeroptical film, leading to under-heating or over-heating portions of thefilm. Localized over-heating of the infrared light absorber by ahigh-energy-flux laser results in charring and other defects in theimaged film.

SUMMARY

The present disclosure relates to stabilized infrared light absorbingdispersions, polyester resins containing these dispersions and polyesterfilms formed from these polyester resins. In particular the presentdisclosure relates to the use of phosphorous-containing dispersants tostabilize infrared light absorbing pigments in the dispersion and toincrease infrared light absorption and improve particle distributionuniformity.

In one aspect, a dispersion includes an infrared light absorbingpigment, a dispersant including phosphorus and a polyol. The infraredlight absorbing pigment includes organo-metallic particles. The infraredlight absorbing pigment absorbs at a selected wavelength in a range of750-1100 nm at least 1.5 times as strongly as in a visible range of500-560 nm. At least 99%, or at least 99.5%, or at least 99.9% of theorgano-metallic particles are less than 1.5 micrometer in size.

In another aspect, a resin includes a polyester material, an infraredlight absorbing pigment dispersed in the polyester material and adispersant comprising phosphorus. The infrared light absorbing pigmentincludes organo-metallic particles. The infrared light absorbing pigmentabsorbs at a selected wavelength in a range of 750-1100 nm at least 1.5times as strongly as in a visible range of 500-560 nm. At least 98%, orat least 99%, or at least 99.5% of the organo-metallic particles areless than 1.5 micrometer in size.

In still another aspect, a resin includes a polyester material, aninfrared light absorbing pigment dispersed in the polyester material anda dispersant comprising phosphorus. The infrared light absorbing pigmentincludes organo-metallic particles. The infrared light absorbing pigmentabsorbs at a selected wavelength in a range of 750-1100 nm at least 1.5times as strongly as in a visible range of 500-560 nm. No more than0.005% of the total volume of the resin includes metal-containingparticles greater than 1.5 micrometers in size.

In a further aspect, a polyester film includes an infrared lightabsorbing pigment dispersed in a polyester film layer. The infraredlight absorbing pigment includes organo-metallic particles and adispersant including phosphorus. The infrared light absorbing pigmentabsorbs at a selected wavelength in a range of 750-1100 nm at least 1.5times as strongly as in a visible range of 500-560 nm. At least 98%, orat least 99%, or at least 99.5% of the organo-metallic particles areless than 1.5 micrometer in size.

In yet a further aspect, a polyester film includes an infrared lightabsorbing pigment dispersed in a polyester film layer. The infraredlight absorbing pigment includes organo-metallic particles and adispersant including phosphorus. The infrared light absorbing pigmentabsorbs at a selected wavelength in a range of 750-1100 nm at least 1.5times as strongly as in a visible range of 500-560 nm. No more than0.005% of the total volume of the film includes metal-containingparticles greater than 1.5 micrometers in size.

These and various other features and advantages will be apparent from areading of the following detailed description.

DETAILED DESCRIPTION

All scientific and technical terms used herein have meanings commonlyused in the art unless otherwise specified. The definitions providedherein are to facilitate understanding of certain terms used frequentlyherein and are not meant to limit the scope of the present disclosure.

Unless otherwise indicated, all numbers expressing feature sizes,amounts, and physical properties used in the specification and claimsare to be understood as being modified in all instances by the term“about.” Accordingly, unless indicated to the contrary, the numericalparameters set forth in the foregoing specification and attached claimsare approximations that can vary depending upon the properties sought tobe obtained by those skilled in the art utilizing the teachingsdisclosed herein.

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5) and any range within that range.

As used in this specification and the appended claims, the singularforms “a”, “an”, and “the” encompass embodiments having pluralreferents, unless the content clearly dictates otherwise.

As used in this specification and the appended claims, the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

As used herein, “have”, “having”, “include”, “including”, “contain”,“containing”, “comprise”, “comprising” or the like are used in theiropen ended sense, and generally mean “including, but not limited to”. Itwill be understood that “consisting essentially of”, “consisting of”,and the like are subsumed in “comprising,” and the like.

The term “pigment” refers to a material loaded above its solubilityresulting in non-dissolved or dissolvable particles.

The term “decomposition temperature” refers to the temperature where asignificant portion of the material degrades. For practical purposes,the decomposition temperature is considered the temperature at which thematerial loses more than 4% of its mass under an inert dry nitrogenatmosphere using a Thermo-Gravimetric Analysis (TGA) under a standardtemperature scan rate of 10 degrees centigrade per minute.

The present disclosure relates to stabilized infrared light absorbingdispersions, polyester resins containing these dispersions and polymerfilms formed from these polyester resins. In particular the presentdisclosure relates to the use of phosphorous-containing dispersants tostabilize infrared light absorbing pigments in the dispersion and toincrease infrared light absorption and improve particle distributionuniformity. The dispersion has a small pigment size with a narrow sizedistribution. The dispersion possesses high infrared light absorption,high visible light transmission, low haze, and temperature stability atresin and film processing temperatures. The dispersion can be used inpolyester synthesis without degrading the polymer. The dispersionpigment has a measurable size distribution in a range from 0.1 to 1.5micrometer or from 0.1 to 1 micrometer where at least 95%, 98%, 99%99.5% or 99.9% of the pigment particles fall within this range. Thisdispersion provides a uniform distribution of pigment to the resinmaterial and resulting formed polyester film while improving itsimagability. In particular, the dispersants described herein enhance theoptical properties of the resulting formed polyester film. The describedphosphorus-containing dispersants can stabilize the infrared lightabsorbing pigments in the dispersions and increase infrared absorptionefficiency through shifting the infrared absorption peak to higherwavelengths and boosting peak absorption. While the present disclosureis not so limited, an appreciation of various aspects of the disclosurewill be gained through a discussion of the examples provided below.

This disclosure generally relates to infrared (IR) light absorbers,dispersants, medium (solvent, or principal liquid-phase component of asuspension), film, and the processes to make them. The infrared lightabsorbers or absorbing pigments include metal containing or metalcomprising pigments, as described below. These pigments can have goodthermal stability at polymer film processing temperature, such as up to300 degrees centigrade or up to 280 degrees centigrade, for example. Themedium (or solvent or principal liquid-phase component of a suspension)is used to disperse the pigment in and as a carrier to bringnon-agglomerated particles to the next processing step. The medium doesnot interfere with the function of other components. In some cases, themedium is a reaction component for a copolyester making reaction. Insome instances, the infrared light absorber, dispersants, and/or mediumbenefit from limited exposure to polymer film processing temperatures,for example, by the addition of a portion of the dispersion after thepolymerization reaction has started.

In many embodiments the medium is a polyol. Polyol is an alcoholcontaining multiple hydroxyl groups, for example ethylene glycol is apolyol containing two hydroxyl groups. The dispersants (or surfactant ordispersing aides) are used to prevent particles from agglomerating orre-agglomeration after separating from a milling process (to form aparticular size distribution of pigment particles, if needed). Thedispersants can have particle binding sites in nonionic, anionic, orcationic groups. In many embodiments the dispersant is an anionicbinding dispersants, more specifically a phosphorus containingdispersants, such as with phosphate and/or phosphoric acid groups. Thedispersants are compatible or soluble in the medium, such as ethyleneglycol. In preferred embodiments, the final dispersion is used in acopolyester making reaction, such as polyethylene terephthalate (PET),copolyethylene terephthalate (coPET) and/or copolyethylene naphthalate(coPEN).

In many embodiments, a dispersion includes an infrared light absorbingpigment, a dispersant including phosphorus and a polyol. The infraredlight absorbing pigment includes organo-metallic particles. The infraredlight absorbing pigment absorbs at a selected wavelength in a range of750 to 1500 nm or from 750 to 1350 nm or from 750 to 1100 nm at least1.5 times as strongly as in a visible range of 500-560 nm. At least 99%or at least 99.5% or at least 99.9% of the organo-metallic particles areless than 1.5 micrometer in size or less than one micrometer in size.

In many embodiments, at least 99% or at least 99.5% or at least 99.9% ofthe organo-metallic particles have a size in a range from 100 nm to 1000nm. Particles above 1.5 micrometers can cause processing problems andfilm irregularities. In addition, particles over 1.5 micrometers in sizecan cause localized over-heating of the large particle, resulting incharring and other defects in a polymer film containing these particles.Particles below 100 nm may, in some cases, be considered an engineerednanoparticle which may not be desirable in some applications.

The organo-metallic particles include a metal. Metals include transitionmetals, alkali and alkaline earth metals, main Group IIIA, IVA and VAmetals, and lanthanides. Lanthanides include La, Ce, Pr, Nd, Sm, Eu, Gd,Tb, Dy, Ho, Er, Tm, Yb, or Lu. In many embodiments the lanthanide is La,Gd, Dy, Er, or Yb. An alkali metal includes Na, K, Rb, or Cs. Analkaline earth metal includes Mg, Ca, Sr, or Ba. In many embodiments thealkaline earth metal is Mg or Ca, A Group IIIA metal includes Al, Ga,In, Tl. In many embodiments the Group IIIA metal is Al, Ga or In. AGroup IVA metal includes Si, Sn or Pb. Si is semi-metal. In manyembodiments the Group IVA metal is Sn. The Group VA metal is Bi.

In many embodiments the metal includes one or more of Ti, V, Cr, Mn, Fe,Co, Ni, Cu, Zn, Zr, Nb, Pd, Ag, Cd, Ta, W, Pt, or Au. In someembodiments the metal includes one or more of Ti, V, Cr, Mn, Fe, Co, Ni,Cu, Zn, Pd, or Pt. In one embodiment the metal includes Cu.

In many embodiments, the organo-metallic particles include aphthalocyanine moiety. The term “phthalocyanine” includesnaphthalocyanine, and the like, and may be substituted or unsubstituted.In some embodiments, the organo-metallic particles include an aromaticring extended phthalocyanine moiety such as naphthalocyanine moiety. Insome other embodiments, the organometallic particles include additionalfunctional group substituted phthalocyanine and naphthalocyanine moietywhere substitutions are on the aromatic phthalocyanine ornaphthalocyanine ring. In yet another embodiments the organo-metallicparticles include one or more of metal containing or metal comprisingphthalocyanines and/or naphthalocyanines such as vanadylnaphthalocyanine, tin naphthalocyanine, lead naphthalocyanine,poly-copper phthalocyanine, zinc naphthalocyanine, halogenated copperpthalocyanines, amine functionalized phthalocyanines- andnaphthalocyanines, and IR absorbing pigments available under the tradedesignation AMAPLAST™ IR 1050, AMAPLAST™ IR 1000, and the like fromColor Chem Intl., Atlanta, Ga. Organo-metallic particles containingphthalocyanines and/or naphthalocyanine moiety are available from: SigmaAldrich, Milwaukee, Wis.; ABCR GmbH and Co. Karlsruhe, Germany; YamamotoChemicals Inc. Tokyo, Japan; and Nippon Shokubai, Osaka, Japan.

The dispersion can include any useful amount of infrared light absorbingpigment (or organo-metallic particles). In many embodiments thedispersion includes at least twice the soluble limit of infrared lightabsorbing pigment (or organo-metallic particles), or at least 10 timesthe soluble limit of infrared light absorbing pigment (ororgano-metallic particles). In many embodiments the dispersion includesat least 1 wt % of the infrared light absorbing pigment (ororgano-metallic particles). In some embodiments the dispersion includesat least 5 wt % of the infrared light absorbing pigment (ororgano-metallic particles).

The presence of metal can be determined in the dispersion or resin orpolymer film, e.g., with the use of ICP-AES (Induction CoupledPlasma—Atomic Emission Spectroscopy). The metal can be determined by anynumber or techniques such as X-ray Fluorescence Spectroscopy, IR, Raman,UV/VIS, NMR, or Mass-Spec. If the sample size is small and the IRabsorbing material is present at a low concentration, a directobservation technique can be utilized. Using either an IR microscope,electron microscopy (in combination with elemental mapping or EELS), orTOF SIMS or ESCA on strategically separated or cut samples to identifythe phase with the IR absorbing material. X-ray scattering may be ableto be used to eliminate salt and oxide species, thus associating thedetected metal with an organo-metallic. With these subtractions formetal salts and oxides, an estimate of the weight loading for theorgano-metallic can be obtained. If the organo-metallic is known, thenthe weight loading of the organo-metallic is simply the weight fractionof the comprised metal divided by the fractional metal content. Forexample, copper naphthalocyanine has about 9.4% copper content (0.094weight fraction) and thus a copper loading of 0.094 weight percent inthe dispersion, resin or film would be a 1% loading of theorganometallic in said material. Copper containing organometallics withpotential absorption in the range of 750-1100 nm are expected to havecopper fractions in the range 0.02-0.14, Other metal comprisingorganometallics are expected to range similarly, as scaled by theiratomic masses relative to copper (63.5 amu). For example, gold (about169 amu) containing useful organometallics would be anticipated to rangefrom 5.3% to 37.3% gold. If an organometallic of unknown structure isisolated, its metal content can be measured directly with ICP-AES. Ifthe organo-metallic is unknown and cannot be isolated, a range oforgano-metallic weight content can still be estimated using thesebounds. Conversion to volume fractions can be obtained with thedensities of the organometallic and the density of the material in whichit is loaded. Such organometallic densities are anticipated to fall inthe range of 1.4 to 2.0 grams per cubic centimeter.

The dispersion includes a phosphorus-containing dispersant. Thisdispersant is soluble in the polyol at a weight % ratio of at least1:100. The dispersion includes the phosphorus-containing dispersant inany useful amount. In many embodiments, the phosphorus-containingdispersant is present in the dispersion in a range from 0.1 to 20 wt %or in a range from 0.1 to 10 wt %. In some cases, thephosphorus-containing dispersant comprises a polyether phosphate ester.

Surprisingly these phosphorus-containing dispersants are not necessarilythermally stable at the processing temperature of the polyester polymeror polyester film. For example some phosphorus-containing dispersantshave a decomposition temperature of 280 degrees centigrade or less andthe processing temperature of some polyester material and film is atleast 280 degrees centigrade. In other examples thephosphorus-containing dispersants has a decomposition temperature of 250degrees centigrade or less and the processing temperature of somepolyester material and film is at least 250 degrees centigrade. Thus itis unusual that the organo-metallic particles remain dispersed in thepolyester polymer or polyester film since the dispersant decomposes atthe polymer processing temperature. As described herein, thephosphorus-containing dispersants apparently stabilize the infraredlight absorbing pigments in the dispersions and increase infraredabsorption efficiency through shifting the infrared absorption peak tohigher wavelengths and boosting peak absorption. In some cases, thephosphorus-containing dispersant can be detected in the resin or thefilm, e.g. by Nuclear Magnetic Resonance (NMR). For example, thephosphorus may be directly observed in some cases. In other cases, knownmoieties in a given dispersant, not normally present in the polymers ofthe resin or film, may be detected. For example, the 1-D proton spectraof the dissolved dispersant, the masterbatch or film, and the rawpolymer can be compared to assign peaks in the masterbatch or filmspectrum to the dispersant or polymer. Using the structural information,the amount can be quantified. If the dispersant contains an NMRsensitive nucleus that is not present in the polymer, a 1-D spectrum ofthat nucleus may be collected and quantified using either an internal orexternal standard. In some cases, the attachment of the moieties to thephosphorous can be confirmed using the multiple bond correlationspectrum (gradient heteronuclear multiple bond correlation experimentalso known as gHMBC), e.g. between the proton and the phosphorus.

Phosphorus-containing dispersants are available, e.g., under the tradedesignation Solplus® or Solsperse® from Lubrizol Corp., Wickliffe Ohioand BYK® or DISPERBYK® from BYK USA, Wallingford Conn. Particularlyuseful phosphorus-containing dispersants include Solsperse® 41000,Solsperse® 27000, Solsperse® 43000, Solsperse® 46000, Solplus® D520,Solplus® D540, BYK®-W 9010, and DISPERBYK®-111.

In some embodiments the resin material includes a pigmentary synergistagent used in conjunction with the phosphorus-containing dispersant. Insome embodiments this synergist agent is a phthalocyanine synergist. Anexemplary phthalocyanine synergist is available under the tradedesignation Solsperse® 5000 (a phthalocyanine synergist available fromLubrizol Corporation, Wickliffe Ohio USA).

The disclosure also relates to a resin material that includes thedispersion described above and this resin can be useful for formingpolymer film, multilayer polymer film, or otherwise formed polymerarticle. The resin can include a polyester material, an infrared lightabsorbing pigment dispersed in the polyester material and a dispersantincluding phosphorus. The resin can include other polymer materials suchas PMMA, syndiotactic PS, PC and PET-PC alloys. The polymer films caninclude other optical elements such as diffuse reflective polarizers.The infrared light absorbing pigment includes organo-metallic particles,as described above. The infrared light absorbing pigment absorbs at aselected wavelength in a range of 750 to 1500 nm or from 750 to 1350 nmor from 750 to 1100 nm at least 1.5 times as strongly as in a visiblerange of 500-560 nm. A particularly useful infrared band is around 1064nm or between 1049-1079 nm, typical of many commercially availableinfrared lasers. In some cases, the infrared light absorbing pigment inthe resin or film absorbs in the band from 1049-1079 nm at least 1.5times as strongly as in a visible range of 500-560 nm. At least 95%, orat least 98%, or at least 99%, or at least 99.5% of the organo-metallicparticles are less than 1.5 micrometer in size or less than onemicrometer in size, as described above.

The resin includes the infrared light absorbing pigment in any usefulamount above the solubility limit. In many embodiments, the infraredlight absorbing pigment is present in the resin in a range from 0.01 to10 wt % or in a range from 0.02 to 5 wt % or in a range from 0.05 to 2wt %.

The disclosure also relates to a polymer film that includes the resindescribed above and this polymer film can be a multilayer polymer filmor a polymeric blend film. In many embodiments the polymer film is apolyester film. The polyester film can include the dispersion describedabove. The infrared light absorbing pigment is dispersed in a polyesterfilm layer, or in a blend film layer comprising a polyester. Theinfrared light absorbing pigment includes organo-metallic particles, asdescribed above. The infrared light absorbing pigment absorbs at aselected wavelength in a range of 750 to 1500 nm or from 750 to 1350 nmor from 750 to 1100 nm at least 1.5 times as strongly as in a visiblerange of 500-560 nm. At least 95%, or at least 98%, or at least 99%, orat least 99.5% of the organo-metallic particles are less than 1.5micrometer in size or less than one micrometer in size, as describedabove.

The polyester film includes the infrared light absorbing pigment in anyuseful amount, in one or more layers, above the solubility limit. Inmany embodiments, the infrared light absorbing pigment is present in thepolymer film in a range from 0.01 to 5 wt % or in a range from 0.02 to 1wt % or in a range from 0.05 to 0.5 wt %.

In many embodiments the polyester film includes a plurality of innerlayers sandwiched between opposing outer layers. The polyester film canbe a multilayer optical film that has been processed (e.g., oriented) toprovide the selective filtering characteristic. Such multilayer opticalfilms are discussed in one or more of: WO2010/075357 (Merrill et al.),“Internally Patterned Multilayer Optical Films Using Spatially SelectiveBirefringence Reduction”; WO 2010/075363 (Merrill et al.), “InternallyPatterned Multilayer Optical Films with Multiple Birefringent Layers”;and WO 2010/075373 (Merrill et al.), “Multilayer Optical Films Suitablefor Bi-Level Internal Patterning”. These references discuss, among otherthings, multilayer optical films having at least some birefringentinterior or inner microlayers, where the multilayer optical film mayinitially be spatially uniform along the plane of the film, but themultilayer optical film is then subjected to localized heating in apattern-wise fashion so as to reduce the birefringence of at least someof the interior layers in one in-plane zone relative to another in-planezone. The reduced birefringence changes the optical transmission andreflection characteristics of the film in the treated areas relative tountreated areas that were not subjected to localized heating. Thenormally incident transmission through, or the normal angle reflectionfrom, the treated areas of the film may increase or decrease by, forexample, 10%, 20%, or 50% or more over a spectral band of interest,e.g., over at least a portion of blue visible wavelengths, relative tountreated areas of the film. The pattern-wise localized heating may becarried out by exposing the multilayer optical film to a suitablepatterned or scanned laser beam or other optical radiation that isabsorbed by the film, or by exposing selected portions of the multilayeroptical film to radiant heat. In any case, the teachings of thesereferences can be used to provide a multilayer optical film suitable foruse as the patterned layer. If desired, the multilayer optical filmsthat have been patterned using these techniques can have little or noabsorptivity over the selected band of interest (e.g. a portion of bluevisible wavelengths) in both the treated and untreated areas, such that,for example, light that is not reflected by the respective portions issubstantially transmitted. In some embodiments the multilayer opticalfilm includes a diffuse reflective polarizer.

Surprising the inner polyester film layers have an average thickness ofless than 100 nm and thus the particle size of the infrared lightabsorbing pigment (as measured in the dispersion) is equal to or greaterthan the thickness of each of these inner layers.

In some embodiments, the polyester film comprises a polymeric blend. Thefilm comprising the blend can be a single, monolithic layer or can be amultilayer. The blend can comprise one or more blend layers. A blendlayer can be an interior layer. The blend layer can comprise theinfrared light absorbing pigment. The polyester blend film can be anoptical film, e.g. a diffuse reflective polarizer or diffusor, that hasbeen processed (e.g., oriented) to provide the diffusive opticalcharacteristic as discussed in WO 2012/003213 (Merrill), “DiffuseReflective Optical Films with Spatially Selective BirefringenceReduction.”

Although various methods can be used, one particularly useful method fordetermining pigment particle size is X-ray tomography. For example,nano-tomography can be used to find small pigment particles, e.g. lessthan a micron. Micro-tomography can be used to find larger particles.e.g. over 1.5 micrometers. Typically, tomography identifies regions ofhigh electron density that can be associated to metal-comprisingparticles, including organometallic particles. Since dust and otherforeign objects can settle on the resin or film surface, only theparticles essentially embedded within the resin or film are theparticles that are considered to be comprised by the resin or filmlayer.

Typically, analysis of the tomography data can provide a sizedistribution of particles. This data can be reduced, e.g. to a volumepercent of particles over 1.5 micrometers, relative to the total volumeof the measured sample. Given an estimate for the weight loading of thepigment, an estimate of the total volume percent of pigment particlesover 1.5 micrometers can be derived. For pigment loadings of 5% or less,the volume percent of particles over 1.5 micrometers relative to thetotal volume of particles can be estimated as the volume percent ofparticles over 1.5 micrometers relative to the total volume of themeasured sample, divided by the weight fraction of the pigment, timesthe ratio of the density of the resin (or polymer film) to the densityof the pigment. The weight fraction of pigment can be estimated throughICP-AES as the weight fraction of metal divided by the weight fractionof metal in the pigment. For example, consider a known polyester resinwith density 1.3 grams per cubic centimeter containing an unknowncopper-containing organometallic pigment with a total copper content of0.03 weight percent (i.e. 0.0003 weight fraction). Given a tomographymeasurement of 0.004 volume percent of particles larger than 1.5micrometers, then the range for the volume percent of these largeparticles on a total pigment basis can be determined by choosing themaximum copper fraction of 0.14 and the minimum pigment density of 1.4grams per cubic centimeter to obtain the upper bound, and by choosingthe minimum copper fraction of 0.02 and the maximum pigment density of2.0 grams per cubic centimeter to obtain the lower bound, resulting in arange of 0.17 to 1.7 volume percent of pigment particles with a sizelarger than 1.5 micrometers; thus, at least 98% of the organo-metallicparticles are less than 1.5 micrometer in size.

Objects and advantages of this disclosure are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this disclosure.

EXAMPLES

All parts, percentages, ratios, etc. in the examples are by weight,unless noted otherwise. In particular, volume percent is used todescribe particle size and distribution. Solvents and other reagentsused were obtained from Sigma-Aldrich Corp., St. Louis, Mo. unlessspecified differently.

Methods

Micro-Tomography

Size distribution can be determined with micro-tomography. In someinstances, a higher resolution nano-tomography can be used. Tomographyidentifies regions of high electron density that can be associated tometal, whereas ICP-AES identifies the metals present. X-raymicrotomography data were collected using a Skyscan 1172 (BrukerMicro-CT, Kontich, Belgium) scanner at X-ray generator settings of 40kilovolts and 240 microamperes. The scanner employed a 10 megapixelHammatsu detector employed at a 4K by 2K resolution and 16 bit grayscale depth. Projected image data were collected at a resolution of 1.5micrometers per detector pixel as the sample was rotated about 180degrees at a step size of 0.20 degrees with each projected imageaccumulated for 1178 milliseconds and 12 averages per collected detectorpane. Scanner data collection was accomplished using Skyscan 1172control software (Bruker Micro-CT, Kontich Belgium, v1.5.9). Theresulting 900 projected images were taken through reconstructionapplying minor corrections to remove the effects of ring artifacts toproduce a stack to 2D slices perpendicular to and along sample datacollection rotation axis. Reconstruction was accomplished using SkyscanNRecon (Bruker Micro-CT, Kontich Belgium, v1.6.5.8) software. Matrix andparticles were segmented as independent volumes by applying anappropriate gray scale threshold and saving these portions asindependent stacks of binary images. Calculation of individual particleand matrix volumes was accomplished using program CTan (Bruker Micro-CT,Kontich Belgium, v1.13.2).

Absorption

Absorption can be measured indirectly by measuring the transmissionspectra through a sufficiently thin sample of material, e.g. using aPerkin-Elmer Lambda 950 Spectrophotomer equipped with an integratingsphere to capture scattered light. Reflection from the thin film overthe wavelengths of interest can be attributable to surface reflectionfrom the surfaces when interior interference stack reflection arenegligible or otherwise absent. The expected transmission to anon-absorbing film can then be calculated based on the surfacereflection attenuation from the Fresnel coefficients using the measuredrefractive index. This is the baseline transmission. The spectra canthen be measured with a spectrophotometer equipped with an integratingsphere (to capture scattered transmission) on the film with theabsorbing pigment. The absorbance at any wavelength is the negativelogarithm of the ratio of the measured transmission to the baselinetransmission. For the dispersion, a stock solution of low enoughconcentration can be made from the dispersion using a suitable solvent.This solution can be placed in a cuvette and spectrally analyzed e.g.using a Lambda 950 spectrophotometer (available from Perkin-Elmer,Waltham, Mass., USA). A reference solution comprising the same mediumwith dispersants, but without the infrared light absorbing pigment, canbe used as a 100% transmission reference. Often a polar solvent is usedto make the stock solution. Potentially useful polar solvents includedimethyl sulfoxide, dimethyl formamide, N-methyl-2-pyrrolidone, dimethylacetamide, phenol, ortho-dichlorobenzene, trichlorobenzene, water,methanol, methyl ethyl ketone, sulfuric acid, trifluoroacetic,tetrahydrofuran, chloroform, and mixtures thereof.

Comparative Example 1

An optical film including a group of interior layers arranged toselectively reflect near infra-red and visible light by constructive ordestructive interference was made by the co-extrusion and orientation ofmulti-layer thermoplastic films in accord with the general methodsdescribed by U.S. Pat. No. 5,882,774 (Jonza et al.), U.S. Pat. No.6,352,761 (Hebrink et al.), U.S. Pat. No. 6,830,713 (Hebrink, et al.),U.S. Pat. No. 6,946,188 (Hebrink, et al.) and International PatentApplication WO 2010/075357 A1 (Merrill, et al.). More specifically aso-called coPEN 55/45 with hexane diol substitution as described inExample 10 of U.S. Pat. No. 6,352,761 was co-extruded with a coPEN 90/10as described in Example 1 of U.S. Pat. No. 6,946,188.

Prior to co-extrusion, a compounded masterbatch of Amaplast® IR-1050, acopper-containing organo-metallic near infra-red absorber (availablefrom ColorChem, Atlanta Ga., USA) was prepared. Copper was not detectedin the virgin coPEN55/45 without the Amaplast® IR-1050. Using InductionCoupled Plasma Atomic Emission Spectroscopy (ICP-AES), the dry Amaplast®IR-1050 was shown to contain 3 weight % copper. The Amaplast® IR-1050was dried at 100° C. and powder fed into the feed throat of a twin-screwextruder equipped with vacuum concurrently with the coPEN 55/45 alsodried for 60 hours at 85° C. to make a pre-compounded masterbatch. Theweight proportion of Amaplast® IR-1050 to coPEN 55/45 fed was 1:99.Under these conditions of loading, the Amaplast® IR-1050 in themasterbatch behaved like a pigment. X-ray micro-tomography was performedon the masterbatch, revealing the presence of large copper-containingparticles. Significantly more than one volume percent of the copperdistribution was associated with particles larger than 1.5 micrometers.More specifically, 0.077 volume % of the total sample comprisedmetal-comprising particles larger than 1.5 micrometers. The loading ofthe pigment was 1 wt %. The density of the Amaplast® IR-1050 pigment wasmeasured as about 1.534 grams per cubic centimeter and the density ofthe pigment is estimated as about 1.6 grams per cubic centimeter. Thusthe volume % of pigment comprising particles greater than 1.5 micronswas estimated to be 6.5%.

CoPEN 90/10 and coPEN 55/45 were extruded and pumped through melt trainsat final setpoints of 282° C. and 266° C. respectively, in a proportionof 10:9 on a weight basis, into a 275 layer feedblock set at 279° C. ThecoPEN 55/45 melt stream was simultaneously fed virgin resin and themasterbatch resin with Amaplast® IR-1050 in a proportion of 2:7. Thismelt stream also comprised a 30-disc stack of 20 micrometer filters,while the other streams had 7 micrometer filter stacks. The coPEN 90/10stream also fed the protective boundary stream comprising about 20% ofthe coPEN 90/10 feed. The feedblock was equipped with a gradient platewith a block factor of 1.15 to create a layer pair thickness gradientthrough the thickness in this amount. The multilayer flow from thefeedblock was combined with two additional co-extruded skin layersstreams set at 274° C. comprising Eastman® Copolyester SA115B (availablefrom Eastman Chemicals, Kingsport Tenn. USA). The two outer skinscomprised about 32% of the construction by weight. The combined streamwas then cast from a die at 279° C. and electrostatically pinned onto aquenching wheel. The cast film showed clear evidence of intermittentmultilayer flow defects, e.g. parabolically shaped flow lines as well asrippling flow bands, mostly concentrated across the middle of the castwidth. When the masterbatch was removed from the feed and replaced withthe same amount of virgin coPEN 55/45 resin to make an equivalent castfilm, the flow defects disappeared. The cast film with Amaplast® IR-1050was subsequently re-heated above the glass transition temperature of thecoPEN 90/10, stretched over rollers in a length orienter to a draw ratioof about 3.7, and then heated to approximately 132° C. and stretchedtransversely to a draw ratio of about 3.8 and then relaxed transverselyto a final draw ratio of about 3.7 in a tenter. The film was heat set atabout 215° C. after stretching, and then wound into a roll of film. Theresulting optical film was approximately 48 micrometers thick. Thenominal loading of copper in the total film construction was thusestimated to be 21.1 ppm.

A portion of the film free of obvious flow defects was analyzed. Atnormal viewing angle, the film was mostly transparent with a grayishhue. At higher off-normal viewing angles, the film shifted to a cyancolor. The transmission spectra of the resulting multilayer reflectingfilm was measured with a Lambda 950 spectrophotometer (available fromPerkin-Elmer, Waltham Mass.). The film exhibited a strong reflectionband, as manifest as a transmission well in the spectrum, between about700 and 800 nanometers.

The film was imagable, e.g. the reflectivity could be patterned, byselective exposure to the output of a pulsed fiber laser with awavelength of 1062 nm (30 W HM series from SPI Lasers, Southampton, UK),e.g. in accord with the methods of International Patent Application WO2010/075357 A1 (Merrill, et al.); however, processing conditions thatsignificantly reduced the reflectivity without significant charringdefects were limited, requiring low laser power and low scan speeds.

Comparative Example 2

A dispersion was made through a media milling process. The dispersant,Solplus® R730 (available from Lubrizol Corporation, Wickliffe Ohio,USA), was soluble in the chosen polyol solvent, ethylene glycol (e.g. asavailable from MEGlobal, Midland Mich., USA), in at least a 1:1proportion, forming a clear solution. This dispersant, Solplus® R730,did not contain phosphorus. The thermal stability of the Solplus® R730was analyzed using a Thermogravimetric Analyzer (TGA Q5000IR) (asavailable from TA Instruments—Waters LLC, New Castle Del., USA). The TGAshowed that over 98 wt % of the dispersant was stable when ramped underdry nitrogen to 250° C. and was over 96 wt % stable under dry nitrogenwhen ramped to 280° C. A mixture of 76.9 wt % solvent ethylene glycol,3.85 wt % dispersant Solplus® R730 and 19.2 wt % organo-metallicabsorber Amaplast® IR-1050 was made by first combining the ethyleneglycol and Solplus® R730 together using a Dispermat CN-10 laboratoryhigh-shear disperser (BYK-Gardner USA, Columbia Md.) until fullydissolved, and then slowly charging in the Amaplast® IR-1050 powder. Themixed dispersion was then milled in a MinCer laboratory media mill(Netzsch, Exton Pa. USA) loaded with 500 grams of a 0.5 mm yttriastabilized zirconia milling media (available from Toray Industries,Tokyo, Japan). The milling proceeded at 4320 rpm. A small amount ofsample was taken out periodically and analyzed in order to monitor themilling progress. A Zetasizer NanoZS (available from MalvernInstruments, Inc., Westborough Mass.) was used to estimate a meanparticle size of about 0.6 micrometers. Subsequent dispersions,similarly made, were filtered using a Roki HT-10 filter (available fromRoki Techno Co., Ltd., Tokyo, JP) with a 2.5 micrometer cut-off Thedispersions rapidly clogged the filters indicating a substantial numberof particles over 2.5 micrometers.

A so-called PET masterbatch with the IR absorbing Amaplast® IR-1050 wassynthesized according to the following procedure: a stainless steel,electrically heated batch reactor was charged with monomers, catalystsand dispersion. The final charge of materials comprised 58.2 weight %dimethyl terephthalate (DMT) (available from Invista, Wichita Kans.USA), 41.0 weight % ethylene glycol (EG) (available from ME Global,Midland Mich. USA), and 0.7 weight % of the dispersion, as well as 116ppm of cobalt diacetate tertrahydrate (available from Shepherd Chemical,Cincinnati Ohio USA), 116 ppm zinc diacetate dihydrate (available fromAvantor Performance Materials, Center Valley Pa. USA), 233 ppm antimonytriacetate (available from Performance Additives, Subang Jaya, SelangorMalaysia) and 251 ppm of triethylphosphonoacetate (TEPA) (available fromMytech Specialty Chemicals Burlington N.C. USA). Initially, the reactorwas charged with everything except the TEPA. Under pressure (239.2 kPa),the mixture was heated to 257° C. with removal of esterificationreaction by-product, methanol. After the methanol was completelyremoved, the TEPA was charged to the reactor. After 5 min of dwell timethe pressure was then gradually reduced to below 500 Pa while heating to279° C. The condensation reaction by-product, ethylene glycol, wascontinuously removed until a resin having an intrinsic viscosity ofabout 0.50 dL/g, as measured in 60/40 wt. % phenol/o-dichlorobenzene at30° C., was produced.

A sample of the resin was dried at 85° C. for 48 hours and then pressedunder nitrogen between glass slides to form a thin film suitable forspectral analysis. The spectra on the film were taken using aPerkin-Elmer Lambda 950. A zero and 100% transmission baselinecorrection was taken with a single glass slide in place to account forsurface reflections from the front and back surfaces, and then thesample pressed between the glass slides was measured. The resultingratio of the average absorbance of the band from 1049-1079 nm and theband from 500-560 nm, taken as the negative logarithms of the averagemeasured fractional transmission (e.g. the % transmission divided by100) was found to be 1.30.

Example 1

A dispersion was made through a media milling process. Thephosphorous-containing dispersant, Solplus® D540 (available fromLubrizol Corporation, Wickliffe Ohio USA), was soluble in the chosenpolyol solvent, ethylene glycol (e.g. as available from MEGlobal,Midland Mich., USA), in at least a 1:1 proportion, forming a clearsolution. Moreover, the thermal stability of the Solplus® D540 wasanalyzed using a Thermogravimetric Analyzer (TGA Q5000IR) (as availablefrom TA Instruments—Waters LLC, New Castle Del., USA). The TGA showedthat over 96 wt % of the dispersant was stable when ramped under drynitrogen to 195° C. The TGA showed that over 38 wt % of the dispersantwas lost when ramped under dry nitrogen to 250° C. and lost over 78 wt %under dry nitrogen when ramped to 280° C. A mixture of 81.37 wt %solvent ethylene glycol, 4.25 wt % dispersant Solplus® D540 and 14.38 wt% organo-metallic absorber Amaplast® IR-1050 was made by first combiningthe ethylene glycol and Solplus® D540 together using a Dispermat CN-10laboratory high-shear disperser (BYK-Gardner USA, Columbia Md.) untilfully dissolved, and then slowly charging in the Amaplast® IR-1050powder. The mixed dispersion was then milled in a LabStar laboratorymedia mill (Netzsch, Exton Pa. USA) loaded with 500 grams of a 0.5 mmyttria stabilized zirconia milling media (available from TorayIndustries, Tokyo, Japan). The milling proceeded at 4320 rpm. A smallamount of sample was taken out periodically and analyzed in order tomonitor the milling progress. The dispersion samples for analysis werefurther diluted in ethylene glycol and the particle size distributionwas measured by a Partica LA-950 Laser Diffraction Particle SizeDistribution Analyzer (available from Horiba, Irvine, Calif. USA)equipped with a MiniFlow Cell. The milling proceeded until the desiredlevel of fineness was achieved as characterized by the particledistribution as measured by the Partica LA-950: a mean particle size ofapproximately 0.3 micrometers was thus achieved; and no measurableportion of the distribution was over 1 micrometers nor under 0.1micrometers. Furthermore, the dispersion was stable without significantsettling prior to use in the subsequent masterbatch resin making.

A stock solution of a suitable solvent, N-methyl-2-pyrrolidone (NMP) asavailable from EMD Millipore, Bedford Mass., was made with 1.0 weight %of the dispersant Solplus® D540. This stock solution was used to make a20 ppm Amaplast solution from the dispersion. This solution was placedin a cuvette and spectrally analyzed from 400 to 1200 nm using a Lambda950 spectrophotometer (available from Perkin-Elmer, Waltham, Mass.,USA). Three samples of this solution were measured. The average maximumabsorbance of these samples were found at 953 nm. The average absorbanceratio at this maximum to the average absorbance across the visible bandfrom 500 to 560 nm was 2.89.

A so-called coPEN 90/10 masterbatch with the IR absorbing Amaplast®IR-1050 was synthesized according to the following procedure: astainless steel, oil jacketed batch reactor was charged with monomersand catalysts. The final charge of materials comprised 55.7 weight %dimethyl 2,6-naphthalene dicarboxylate (NDC) (available from BP AmocoNaperville Ill. USA), 4.9 weight % dimethyl terephthalate (DMT)(available from Invista, Wichita Kans. USA), 34.8 weight % ethyleneglycol (EG) (available from ME Global, Midland Mich. USA), and 4.5weight % of the dispersion, as well as 121 ppm of cobalt diacetatetertrahydrate (available from Shepherd Chemical, Cincinnati Ohio USA),121 ppm zinc diacetate dihydrate (available from Avantor PerformanceMaterials, Center Valley Pa. USA), 303 ppm antimony triacetate(available from Performance Additives, Subang Jaya, Selangor Malaysia)and 242 ppm of triethylphosphonoacetate (TEPA) (available from MytechSpecialty Chemicals Burlington N.C. USA). Initially, the reactor wascharged with everything except the TEPA and the dispersion. Underpressure (239.2 kPa), the mixture was heated to 257° C. with removal ofesterification reaction by-product, methanol. After the methanol wascompletely removed, the TEPA was charged to the reactor. After 5 min ofdwell time the pressure was gradually reduce to below 500 Pa and thedispersion was charged under pressure raising the kettle pressure to115.1 kPa. After 5 min of dwell time the pressure was then graduallyreduced to below 500 Pa while heating to 279° C. The condensationreaction by-product, ethylene glycol, was continuously removed until aresin having an intrinsic viscosity of about 0.50 dL/g, as measured in60/40 wt. % phenol/o-dichlorobenzene at 30° C., was produced.

A thin film of resin made was captured during the kettle drain andanalyzed. Reflection from the thin film over the wavelengths of interestwas essentially attributable to surface reflection from the surfaces.The expected transmission, based on the surface reflection attenuationas calculable from the Fresnel coefficients using the measuredrefractive index, over a +/−15 nm band about 1064 nm is 89.3% and is88.2% at 530 nm. The spectra on the film were taken using a Perkin-ElmerLambda 950. The resulting ratio of the average absorbance of the bandfrom 1049-1079 nm and the band from 500-560 nm was found to be 1.945.When the absorbance peak value around 1000 nm was used, the ratio withthe visible band from 500-560 nm was about 2.26.

Under these conditions of loading, the Amaplast® IR-1050 in themasterbatch behaved like a pigment. Using Induction Coupled PlasmaAtomic Emission Spectroscopy (ICP), the dry Amaplast® IR-1050 was shownto contain 3 weight % copper. Using ICP, the masterbatch was estimatedto contain 0.026 wt % copper. X-ray micro-tomography was performed onthe masterbatch, revealing the presence of very few, large particlescontaining copper. At least 99.5% of the organo-metallic particles wereless than 1.5 micrometer in size. More specifically, 0.004 volume % ofthe total sample comprised metal-comprising particles larger than 1.5micrometers. The density of the resin is estimated as about 1.3 gramsper cubic centimeter and the density of the AMAPLAST® IR-1050 pigmentwas measured as about 1.534 grams per cubic centimeter. Thus the volume% of pigment comprising particles greater than 1.5 microns was estimatedto be 0.39%.

The masterbatch resin was furthermore analyzed using NMR to detect thepresence of remaining phosphorus-containing dispersant. Three differentanalyses were completed. The first was a 1D phosphorus spectrum, thesecond was a 1D proton spectrum and the third was a multiple bondcorrelation spectrum between the proton and the phosphorus (gradientheteronuclear multiple bond correlation experiment also known as gHMBC).In each case, a portion of the masterbatch resin was dissolved in a 3:1volumetric mixture of deuterated trifluoroacetic acid (d-TFA):deuterated chloroform (CDCl3) in a two-dram vial. The sample wastransferred to a Wilmad economy grade 5 mm borosiliate NMR tube. The NMRtube was placed in a spinner and pneumatically inserted into a Bruker500 MHz Avance NMR spectrometer equipped with a cryogenically cooledbroad-band NMR probe head. After locking and shimming operations werecompleted using the deuterium of the CDCl3, the spectra were collected.In the case of the 1D phosphorous spectrum, the data were collectedusing a 30° pulse width. 128 transients of 128 k points were collectedusing an approximately 1 second acquisition time with a 2 second recycledelay under constant 1H decoupling. The data were Fourier Transformed(FT) after 20 Hz of exponential apodisation, and zero filling to 256 kpoints. No linear prediction was used. A clear 1D phosphorous peak wasapparent. In the case of the one dimensional (1-D) proton NMR spectrum,the data were collected using a 15° pulse width. 128 transients of 32 kpoints were collected using at an approximately 4 second acquisitiontime with no recycle delay. The data were Fourier Transformed (FT)without apodisation, linear prediction, or zero filling. Comparison ofthe dispersant, pure polymer, and dispersant-containing polymer, permitsdetection and quantification of the dispersant in the polymer. In thiscase, the peak at 3.9 ppm was assigned to the known polyethylene glycolmoieties in the dispersant. This peak is not observed in the polymerwithout the dispersant. In the case of the 1H{31P} gHMBC, 128 transientswere collected of 1024 points each. A recycle delay of 1 seconds wasused. The data were Fourier Transformed in the direct dimension afterapodization with a shifted sine bell. No zero filling or linearprediction was used in the direct dimension. The indirect dimension wasFourier Transformed after linear prediction to 1024 points andapodization with a shifted Sine Bell. The data show a clear correlationassigned to the phosphate ester of the dispersant. In this manner, themasterbatch resin was shown to still comprise at least some of theSolplus® D540 dispersant.

Using this masterbatch, a laser-imagable optical film comprising a groupof interior layers arranged to selectively reflect near infra-red andvisible light by constructive or destructive interference was made bythe co-extrusion and orientation of multi-layer thermoplastic films inaccord with the general methods described by U.S. Pat. No. 5,882,774(Jonza et al.), U.S. Pat. No. 6,352,761 (Hebrink et al.), U.S. Pat. No.6,830,713 (Hebrink, et al.), U.S. Pat. No. 6,946,188 (Hebrink, et al.)and International Patent Application WO 2010/075357 A1 (Merrill, etal.). More specifically a coPET with sodium sulfateisophthalate asdescribed in Example 5 as polyester K of Patent Application WO2007/149955 A2 (Liu, et al henceforth referred to as CoPET-1 wasco-extruded with a coPEN 90/10 as described in Example 1 of U.S. Pat.No. 6,946,188.

CoPEN 90/10 and coPET-1 were extruded and pumped through melt trains atfinal setpoints of 274° C. and 260° C. respectively, in a proportion of3:4 on a weight basis, into a 275 layer feedblock set at 279° C. ThecoPEN 90/10 melt stream was simultaneously fed virgin resin and themasterbatch resin with Amaplast® IR-1050 in a proportion of 3:1. ThecoPET-1 stream also fed the protective boundary stream comprising about20% of the coPET-1 feed. The feedblock was equipped with a gradientplate with a block factor of 1.5 to create a layer pair thicknessgradient through the thickness in this amount. The multilayer flow fromthe feedblock was combined with two additional co-extruded skin layersstreams set at 274° C. of coPEN 90/10 with 0.1 wt % synthetic fumedamorphous silica as a slip agent. The two outer skins comprised about 18weight % of the film construction. The combined stream was then castfrom a die at 279° C. and electrostatically pinned onto a quenchingwheel. The cast film showed no evidence of flow defects. The cast filmwith Amaplast® IR-1050 was subsequently re-heated above the glasstransition temperature of the coPEN 90/10, stretched over rollers in alength orienter to a draw ratio of about 3.7, and then heated toapproximately 125° C. and stretched transversely to a draw ratio ofabout 3.5 and then slightly relaxed transversely to a final draw ratioof just under 3.5 in a tenter. The film was heat set at about 238° C.after stretching, and then wound into a roll of film. The resultingoptical film was approximately 69 micrometers thick. The nominal loadingof copper in the total film construction, attributable to the Amaplast®IR-1050, was thus estimated to be 24.3 ppm.

The film was a broad-band reflector with a silver appearance at normaland off-normal viewing angles. The transmission spectra of the resultingmultilayer reflecting film was measured with a Lambda 950spectrophotometer (available from Perkin-Elmer, Waltham Mass.). The filmexhibited a strong normal incidence reflection band, as manifest as atransmission well in the spectrum with measured transmission rangingfrom about 1% to 12% between about 400 and 900 nanometers. Thetransmission of the film was clearly reduced in a band about 1064 nmrelative to the expected baseline transmission without the Amaplast®IR-1050 absorber, clearly indicating the presence of thisorgano-metallic IR-absorbing pigment. Using ICP, the film: no largemetal-comprising particles were detected in the interior of the film.Thus, at least 99.5% of the organo-metallic particles were less than 1.5micrometer in size.

The film was furthermore analyzed using NMR to detect the presence ofremaining phosphorus-containing dispersant in a similar manner to themethod used on the master batch resin. Again, a clear phosphorousspectrum was apparent. As in the case of the masterbatch resin, for the1D proton spectrum, the 3.9 ppm chemical shift was assigned to thepolyethylene glycol moieties of the residual dispersant. A 0.25 cm2sample of the film was dissolved in a 3:1 volumetric mixture ofdeuterated trifluoroacetic acid (d-TFA): deuterated chloroform (CDCl3)in a two-dram vial. The sample was transferred to a Wilmad economy grade5 mm borosiliate NMR tube. The NMR tube was placed in a spinner andpneumatically inserted into a Bruker 500 MHz Avance NMR spectrometerequipped with a cryogenically cooled broad-band NMR probe head. Afterlocking and shimming operations were completed using the deuterium ofthe CDCl3, one dimensional (1-D) proton NMR data were collected using a15° pulse width. 128 transients of 32 k points were collected using anapproximately 4 second acquisition time with no recycle delay. The datawere Fourier Transformed (FT) without apodisation, linear prediction, orzero filling. Again, the 3.9 ppm chemical shift peak was observed abovethe baseline. In this manner, the film was shown to still comprise atleast some of the Solplus® D540 dispersant.

The film was imagable, e.g. the reflectivity could be patterned, byselective exposure to the output of a pulsed fiber laser with awavelength of 1062 nm (30W HM series from SPI Lasers, Southampton, UK),e.g. in accord with the methods of International Patent Application WO2010/075357 A1 (Merrill, et al.). The laser was impinged on the side ofthe film containing the thinner layers of the optical stack. Significantreflectivity reduction (increases over) was accomplished withoutcharring or other defects at a pulse rate (repetition rate) of 250 kHz,and an average power of 5.4 watts. The output of the laser was fiberdelivered to a hurrySCAN 25 galvanometer scanner (SCANLAB AG, Puccheim,Germany) and focused using an f-theta lens with a numerical aperture of0.15 (Sill Optics GmbH, Wendelstein, Germany). In order to minimizelaser damage to the films, the focal point of the f-theta lens waslocated approximately 8 mm above the surface of the samples. The laserbeam was manipulated with the galvanometer scanner to produce 4 mm×4 mmsquares of exposed lines on the samples at each laser condition, withindividual scan lines separated by a distance of 100 micrometers at ascan rate of 200 mm/sec.

Example 2

A cast film similar to the pre-cursor cast film of Example 1 was made;however, a 1:2 loading of masterbatch to virgin coPEN 90/10 was fed intothe feedblock and thicker skins, comprising 36 weight % of the finalconstruction was made.

Reflection from the cast web over the wavelengths of interest wereessentially attributable to surface reflection from the surfaces. Theexpected transmission, based on the surface reflection attenuation ascalculable from the Fresnel coefficients using the measured refractiveindex, over a +/−15 nm band about 1064 nm is 89.3% and is 88.2% at 530nm. The spectra on the final cast film were taken using a Perkin-ElmerLambda 950. The resulting ratio of the average absorbance of the bandfrom 1049-1079 nm and the band from 500-560 nm was found to be 2.077.

The cast film was stretched to make an oriented film similarly to thedrawn film of example 1. The film exhibited a strong normal incidencereflection band, as manifest as a transmission well in the spectrum,between about 400 and 900 nanometers. The transmission of the film wasclearly reduced in a band about 1064 nm relative to the expectedbaseline transmission without the Amaplast® IR-1050 absorber.

Using a laser at 1064 nm, the final drawn film was imagable, e.g. thereflectivity could be patterned, e.g. in accord with the methods of andInternational Patent Application WO 2010/075357 A1 (Merrill, et al.).

Example 3

A dispersion was made through a media milling process. Thephosphorous-containing dispersant, Solplus® D540 (available fromLubrizol Corporation, Wickliffe Ohio USA), was soluble in the chosenpolyol solvent, ethylene glycol (e.g. as available from MEGlobal,Midland Mich., USA), in at least a 1:1 proportion, forming a clearsolution. A mixture of 84.13 wt % solvent ethylene glycol, 3.44 wt %dispersant Solplus® D540, 11.47 wt % organo-metallic absorber Amaplast®IR-1050 and 0.96 wt % co-dispersant Solsperse® 5000 (a phthalocyaninesynergist available from Lubrizol Corporation, Wickliffe Ohio USA) wasmade by first combining the ethylene glycol, Solplus® D540 andSolsperse® 5000 together using a Dispermat CN-10 laboratory high-sheardisperser (BYK-Gardner USA, Columbia Md.) until fully dissolved, andthen slowly charging in the Amaplast® IR-1050 powder. The mixeddispersion was then milled in a LabStar laboratory media mill (Netzsch,Exton Pa. USA) loaded with 1700 grams of a 0.5 mm yttria stabilizedzirconia milling media (available from Toray Industries, Tokyo, Japan).The milling proceeded at 3500 rpm. A small amount of sample was takenout periodically and analyzed in order to monitor the milling progress.The dispersion samples for analysis were further diluted in ethyleneglycol and the particle size distribution was measured by a ParticaLA-950 Laser Diffraction Particle Size Distribution Analyzer (availablefrom Horiba, Irvine, Calif. USA) equipped with a MiniFlow Cell. Themilling proceeded until the desired level of fineness was achieved ascharacterized by the particle distribution as measured by the ParticaLA-950: a mean particle size of approximately 0.16 micrometers was thusachieved; and no measurable portion of the distribution was over 1micrometer nor under 0.1 micrometers. Furthermore, the dispersion wasstable without significant settling prior to use in the subsequentmasterbatch resin making.

A polyethylene terephthalate (PET) masterbatch with the IR absorbingAmaplast® IR-1050 was synthesized according to the following procedure:a stainless steel, electrically heated batch reactor was charged withmonomers, stabilizer and catalysts. The final charge of materialscomprised 54.7 weight % dimethyl terephthalate (DMT) (available fromInvista, Wichita Kans. USA), 38.5 weight % ethylene glycol (EG)(available from ME Global, Midland Mich. USA), and 6.7 weight % of thedispersion, as well as 109 ppm of cobalt diacetate tetrahydrate(available from Shepherd Chemical, Cincinnati Ohio USA), 109 ppm zincdiacetate dihydrate (available from Avantor Performance Materials,Center Valley, Pa. USA), 274 ppm antimony triacetate (available fromPerformance Additives, Subang Jaya, Selangor Malaysia) and 219 ppm oftriethylphosphonoacetate (TEPA) (available from Mytech SpecialtyChemicals Burlington N.C. USA). Initially, the reactor was charged witheverything except the TEPA and the dispersion. Under pressure (239.2kPa), the mixture was heated to 257° C. with removal of esterificationreaction by-product, methanol. After the methanol was completelyremoved, the TEPA was charged to the reactor. After 5 min of dwell time,the dispersion was charged under pressure. After 5 min of dwell time thepressure was then gradually reduced to below 500 Pa while heating to279° C. The condensation reaction by-product, ethylene glycol, wascontinuously removed until a resin having an intrinsic viscosity ofabout 0.50 dL/g, as measured in 60/40 wt. % phenol/o-dichlorobenzene at30° C., was produced.

A sample of the resin was dried at 85° C. for 48 hours and then pressedunder nitrogen between glass slides to form a thin film suitable forspectral analysis. The spectra on the film were taken using aPerkin-Elmer Lambda 950. A zero and 100% transmission baselinecorrection was taken with a single glass slide in place to account forsurface reflections from the front and back surfaces, and then thesample pressed between the glass slides was measured. The resultingratio of the average absorbance of the band from 1049-1079 nm and theband from 500-560 nm, taken as the negative logarithms of the averagemeasured fractional transmissions (e.g. the % transmissions divided by100) was found to be 1.64.

Under these conditions of loading, the Amaplast® IR-1050 in themasterbatch behaved like a pigment. Using Induction Coupled PlasmaAtomic Emission Spectroscopy (ICP), the dry Amaplast® IR-1050 and drySolsperset 5000 were shown to contain 3 and 5.45 weight % copper,respectively. Using ICP, the masterbatch was estimated to contain 0.0342weight % copper from Amaplast® IR-1050 (i.e. approximately 1.1 wt %loading Amaplast® IR-1050) and 0.0051 weight % copper from Solsperset5000.

Using this masterbatch, a laser-imagable optical film comprising a groupof interior layers arranged to selectively reflect near infra-red andvisible light by constructive or destructive interference was made bythe co-extrusion and orientation of multi-layer thermoplastic films inaccord with the general methods described by U.S. Pat. No. 5,882,774(Jonza et al.), U.S. Pat. No. 6,352,761 (Hebrink et al.), U.S. Pat. No.6,830,713 (Hebrink, et al.), U.S. Pat. No. 6,946,188 (Hebrink, et al.)and International Patent Application WO 2010/075357 A1 (Merrill, etal.). More specifically so-called coPMMA, Atoglas prd-510A (Availablefrom Arkema, Philadelphia Pa. USA) was co-extruded with PET.

PET, Tairilin AA48, (available from Nanya, Lake City S.C. USA) andcoPMMA were extruded and pumped through melt trains at final setpointsof 274° C. and 260° C. respectively, in a proportion of 10:9 on a weightbasis, into a 151 layer feedblock set at 274° C. The PET melt stream wassimultaneously fed the virgin PET resin and the PET masterbatch resinwith Amaplast™ IR-1050 in a proportion of 8:1. The PET stream also fedthe protective boundary stream comprising about 8% of the coPET-1 feed.The feedblock was equipped with a gradient plate with a block factor of1.15 to create a layer pair thickness gradient through the thickness inthis amount. The multilayer flow from the feedblock was combined withtwo additional co-extruded skin layers streams set at 274° C. of PET,Tairilin 1N404. The two outer skins comprised about 57 weight % of thefilm construction. The combined stream was then cast from a die at 275°C. and electrostatically pinned onto a quenching wheel to form a castfilm 490 micrometers thick. The cast film was a neutral gray inappearance.

The cast film with Amaplast® IR-1050 was subsequently stretched in aKARO IV laboratory stretcher (available from Bruekner, Portsmouth N.H.USA). The cast web was pre-heated for 60 seconds at 95° C. and thenstretched at a uniform separation speed of the grippers corresponding toan initial strain rate 5% per second to draw ratios of 4.7 and 5.0 intwo in-plane orthogonal directions. The films was subsequently heat setafter drawing at heat set at 180° C. after stretching. The resultingoptical film was approximately 20 micrometers thick.

The film was a far-red, near-infra reflector. The transmission spectraof the resulting multilayer reflecting film was measured with a Lambda950 spectrophotometer (available from Perkin-Elmer, Waltham Mass.). Thefilm exhibited a strong normal incidence reflection band, as manifest asa transmission well in the spectrum, between about 660 and 740nanometers, with a minimum transmission under 2%. The transmission ofthe film was discernably reduced in a band about 1064 nm relative to theexpected baseline transmission without the Amaplast® IR-1050 absorber.

The film was imagable, e.g. the reflectivity could be patterned at muchhigher power, without charring, than the film of Comparative Example 2,by selective exposure to the output of a pulsed fiber laser with awavelength of 1062 nm (30 W HM series from SPI Lasers, Southampton, UK),e.g. in accord with the methods of International Patent Application WO2010/075357 A1 (Merrill, et al.).

Thus, embodiments of STABILIZED INFRARED ABSORBING DISPERSIONS aredisclosed.

All references and publications cited herein are expressly incorporatedherein by reference in their entirety into this disclosure, except tothe extent they may directly contradict this disclosure. Althoughspecific embodiments have been illustrated and described herein, it willbe appreciated by those of ordinary skill in the art that a variety ofalternate and/or equivalent implementations can be substituted for thespecific embodiments shown and described without departing from thescope of the present disclosure. This application is intended to coverany adaptations or variations of the specific embodiments discussedherein. Therefore, it is intended that this disclosure be limited onlyby the claims and the equivalents thereof. The disclosed embodiments arepresented for purposes of illustration and not limitation.

What is claimed is:
 1. A resin comprising: a polyester material having aprocessing temperature of at least 250 degrees centigrade; an infraredlight absorbing pigment dispersed in the polyester material, theinfrared light absorbing pigment comprising organo-metallic particles,the organo-metallic particles comprising metal and an organic moiety,the metal covalently bonded to one or more atoms of the organic moiety,the infrared light absorbing pigment absorbs at a selected wavelength ina range of 750-1100 nm at least 1.5 times as strongly as in a visiblerange of 500-560 nm, at least 98% of the organo-metallic particles areless than 1.5 micrometer in size; and a dispersant comprisingphosphorus; wherein the resin comprises the pigment in an amount aboveits solubility limit.
 2. The resin according to claim 1, wherein theorgano-metallic particles comprise Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn,Zr, Nb, Pd, Ag, Cd, Ta, W, Pt, or Au.
 3. The resin according to claim 1,wherein the at least 98% of the organo-metallic particles have a size ina range from 100 nm to 1000 nm.
 4. The resin according to claim 1,wherein the infrared light absorbing pigment comprises copper.
 5. Theresin according to claim 1, wherein the infrared light absorbing pigmentcomprises phthalocyanine moieties.
 6. The resin according to claim 1,wherein the resin comprises 0.01 to 5 wt % infrared light absorbingpigment.
 7. The resin according to claim 1, wherein the resin comprisesa phthalocyanine synergist.
 8. The resin according to claim 1, whereinthe polyester material has a processing temperature of at least 280degrees centigrade.
 9. The resin according to claim 8 wherein thepolyester material comprises polyethylene terephthalate, copolyethyleneterephthalate or copolyethylene naphthalate.
 10. The resin according toclaim 1, wherein the resin further comprises poly(methyl methacrylate),syndiotactic polystyrene, polycarbonate or polyethyleneterephthalate-polycarbonate alloys.
 11. A polymer melt comprising: apolyester material; an infrared light absorbing pigment dispersed in thepolyester material, the infrared light absorbing pigment comprisingorgano-metallic particles, the organo-metallic particles comprisingmetal and an organic moiety, the metal covalently bonded to one or moreatoms of the organic moiety, the infrared light absorbing pigmentabsorbs at a selected wavelength in a range of 750-1100 nm at least 1.5times as strongly as in a visible range of 500-560 nm, at least 98% ofthe organo-metallic particles are less than 1.5 micrometer in size; anda dispersant comprising phosphorus; wherein the polymer melt is at atemperature of at least 250 degrees centigrade.